Motor fuel production



Oct. 14,- 1941. H. v`. ATwELL MOTOR FUEL PRODUCTION Filed oct. so. 1937Patented Oct, 14,! 1941 UNITED STATES PATENT OFFICE f i 2,253,839 f lMoron rum. rnonuc'rxox umm v. mwen, wma mms, N. Y., mimora goa-c. mationof Delaware Appuunn october 3o, 1937, serai No. 171,919 o 4 claims. (ci:19e-s) This invention relates to the production of normally liquidhydrocarbons from a gaseous mixture consisting essentially of carbonmonoxide and hydrogen. More particularly, the invention relates to theproduction of normally liquid hydrocarbons from carbon monoxide andhydrogen and the treatment thereof to produce a gasoline of highanti-knock value.

mm, Inc., New

tion of the resulting products to' form aromatics,

alkylation reactions between. gaseous constitu- The normally liquidhydrocarbons produced by the reaction of carbon monoxide and hydrogenordinarily include substantial proportions of hydrocarbons in thegasoline boiling range. However, the fraction corresponding to thevgasoline boiling'range recovered from the synthesis reaction productsis very low in anti-knock value and therefore Agenerally unsuitable assuch; as, The treatment of this niagasoline motor fuel. terial byapplication'of elevated conditions of temperature and pressure toimprove its antiknock value results in the production of largequantities of gas and accompanying low recovery of useful products. Theimprovement inI antiknock value by this means may not justify the lossesinvolved in the process. This may be caused by the relative absence ofaromatic constituents in the reaction products of carbonr monoxide andhydrogen, this condition being alsoresppnsible, in part at least, forthe initial low anti-knock value of the motor fuel fraction.

It is an object of the' present invention to provide a means fortreating normally liquid prod-`v ucts obtained by the reaction of carbonmonoxide and hydrogen to produce therefrom a gasoline motor fuel of highanti-knock value, with maximum recovery of useful products.

The invention contemplates the separation of a gasoline fraction fromthe reaction products of ents and between gaseous and normallyiiquidconstituents, etc., although the invention is not to be limited by suchtheoretical considerations. The reaction products are treated toseparate therefrom a gasoline fraction and a normally gaseous fractionpredominating in C3 and C4 hydrocarbons which are in part at leastadmixed with the normally liquid fraction undergoing conversiontreatment as described. Cz hydrocarbons and lighter products may berecovered and converted to a carbon monoxide-hydrogen mixture bysuitable4 catalytic oxidation. The accompanying drawing is adiagrammatic view in elevation of apparatus suitable for carrying outthe present invention. The invention will be further described withreference to the specific embodiment illustrated by the drawing, but itis to'be understood that the invention is not limited thereby but iscapable of other embodiments which may be beyond the'physicallimitations of the apparatus illustrated.

In the embodiment of the invention as illustrated in the drawing thecarbon monoxide-hydrogen mixture is produced by the catalytic oxidationof hydrocarbon gases, particularly methane and C: hydrocarbons, it beingunderstood that the invention is not limited to the treatment ofhydrocarbons produced by the reaction of a mixture of carbon monoxideand hydrogen obtained in any particular manner. Referring to thedrawing, a stream of gaseous hydrocarbons predominatingv in methane andCz hydrocarbons provided with valve 2. A second pipe line 3 pro'- carbonmonoxide and hydrogen and the subjection of thegasoline fraction toelevated conditions of temperature and pressure in the presence v of asubstantial proportion of convertible vnormally gaseous hydrocarbonsproduced in ther process, having three and four carbon atoms permolecule, hereafter referred to as Cs and C4 hytor fuel of highanti-knock value. tions of temperature and pressure preferably are videdvwith valve 4 is provided for the introduc-l tion of'oxygen. Lines Iand. 3 join to form line 5, and the mixture of oxygen and hydrocarbongases suitable to produce the desired mixture of carbon monoxide andhydrogen is produced by suitable manipulations of valves 2 and 4. Line 5connects with a catalytic oxidation chamber 6 which may consist of alplurality of tubes arranged in parallel between suitable headers andcontaining a mixture of 90 parts nickel oxide and 10 parts of a promotersuch as thoria on a suitsufliciently drastic to effect cracking ofnormally liquid constituents, and the reactions which result in theproduction of high anti-knock motor fuel probably are, in addition tocracking, polymerization of normally gaseous constituents,dehydrogenation of parailinic constituents, cyclization of aliphaticconstituents and dehydrogena- 55 temperature byl a suitable insulationof the reacbe in the range of 900 to 1500* F. Ordinarily able carriersuch as fire clay or magnesia. The temperature for maximum oxidationwill vary with the catalyst employed but ordinarily should atmosphericpressure is employed. The oxidation reaction is only slightly exothermicso that it. may be necessary to maintain the reaction,

tion chamber. Preferably, however, the catalyst is suitably maintainedin tubes 8 through which sage of heating or cooling uids as necessary onthe outside of the tubes to maintain the desired reaction temperatureand toI obtain maximum contact of the catalyst and gaseous mixture thereaction mixture is passed to permit the pasthrough the subdivision ofthe gaseous stream in the plurality of tubes 8 of the oxidation chamber.Preheating of the gaseous mixture entering oxidation chamber 6 asdesired may be effected by the provision of heater 'I in line 5.

The oxidation reaction products emerge from chamber B by means of line 9and may be treated to remove undesirable components such as sulphurcompounds and to adjust the ratio of carbon monoxide to hydrogen, bymeans not shown. The oxidation reaction products suitably may passthrough a heat exchanger I0 located in line 9 wherein they pass inindirect contact with a hydrocarbon stream produced in the system toeffect cooling of the oxidation reaction products and heating of thehydrocarbon stream. If necessary they may be further cooled to the exacttemperature required for the succeedingoperation by passage throughcooler II, also located in line 9.

After emerging from cooler II the oxidation reaction products, whichconsist essentially of carbon monoxide and hydrogen in the desiredratio, are passed through a synthesis chamber l2 for the production ofhydrocarbons by the reaction of carbon monoxide and hydrogen.

Synthesis chamber I2 suitably consists of a plurality of tubes I3arranged in parallel between suitable headers and maintained in a fluidbath cross sectional dimension greatly in excess of the other whereby arelatively narrow passageway is .provided in each. The tubes I3 areprovided with a suitable catalyst for the conversion of the carbonmonoxide and hydrogen to hydrocarbons of greater molecular weight. Forexample, the catalyst may consist of metallic cobalt deposited on acarrier such as kieselguhr together with a promoter such as thoria. Thegases should be maintained at a temperature of approximately 365 to 415F. at atmospheric pressure for maximum conversion. The reaction isexothermic, and the tubes I3 are immersed in a bath of oil or othersuitable fluid which serves. to remove thegexothermic heat of reaction.Means not shoiki are provided. to circulate and cool the bath of oil,etc. to maintain the desired temperature.

The rate of this reaction is relatively low whereby it is necessary toprovide a relatively long time of contact to secure complete conversionof the carbon monoxide and hydrogen. This may be done by providing asingle large chamber or, preferably, by providing aplurality of chamberswith removal of liquids formed from the stream after passage througheach chamber. For purposes of illustration the present drawing includestwo such chambers, but it is to be understood that any suitable numbermay be employed without departing from the method of operationillustrated.

The reaction products from synthesis chamber I2 may be withdrawntherefrom through line I4 which connects with a fractionator I5. Infractionator I5 conditions of temperature and pressure may be maintainedto effect condensation of normally liquid hydrocarbons and a desiredportion of the normally gaseous hydrocarbons. To facilitatefractionation superatmospheric pressure may be maintained infractionator I5, In this case a compressor I6 is provided in line I4 toforce the gases therein into the fractionator I5. Heating means such asa heating coil I1 and cooling means such as cooling coil I8 maybeprovided in the bottom and top, respectively, of fractionator I5 toeffect the desired separation.

'I'he gases uncondensed in fractionator I5 are withdrawn from the upperportion of fractionator I5 through line I9 provided with control valve20. Heating means 2l is interposed in line I8 to raise the gaseousmixture in line I9 to the desired reaction temperature, e. g., 365 to415 F. Be-

yond heating means 2| line I 9 connects with a second synthesis chamber22 which n ay be identical in construction with synthesis chamber I2including the same type of catalyst in a plurality of tubes so that nodetaileddescription of this chamber will be given. Synthesis chambers I2and 22 represent the rst and last of a series of such chambers which mayexceed two in number, the additional chambers being connected in seriesbetween chambers I2 and 22 with provision for removal of liquid productsafter each chamber in the manner illustrated in connection` with chamberI2.

The reaction products are withdrawn from chamber 22 through line 23 andconsist of any unreacted hydrogen and carbon monoxide,` normally liquidhydrocarbons formed in chamber '22, normally gaseous hydrocarbons formedin chamber 22 and normally gaseous hydrocarbons formed in chamber I2 andnot removed by Vcondensation in fractionator I5. Line 23 connects with afractionator 24, and the reaction products from chamber 22 areintroduced therein for separation as desired. Superatmospheric pressuremay be employed in fractionator 24 to facilitate the desired separation,and in this case a compressor. 25 is provided in line 23 to force thereaction products from line 23 into fractionator 24. Line 26 providedwith a pump 21 connects the bottom of fractionator I5 with anintermediate point in fractionator 24 whereby the liquid fractionseparated in fractionator I5 is introduced into fractionator 24 forfurther treatment therein.

In contrast with the conditions obtaining in fractionator I5.fractionator 24 is maintained under conditions of temperature andpressure suitable to effect separation and collection of a. liquidfraction consisting of those reaction products boiling above the boilingrange of the fraction desired for further treatment in the process toproduce a high anti-knock motor fuel. For example, fractionator 24 maybe operated under conditions, suitable to eiect condensation and'separation of constituents boiling substantially above 400 F., or thefractionator may be operated to eil'ect the passage overhead of agaseous and vaporous mixture including an appreciable proportion ofconstituents boiling above 400 F. In any case, however, the mixture ofvapors and gases passing overhead from fractionator 24 should be limitedin the amount of material higher boiling than 400 F. whereby a normallyliquid condensate produced therefrom contains at most a minor proportionof constituents boiling above the gasoline boiling range. To eiect thedesired fractionation of the reaction products introduced intofractionator 24 through lines 23 and 2E, heating means such as heatingcoil 28 and cooling means such as cooling coil 29 may be provided in thelower and upper portions, respectively, of fractionator 24. The liquidcondensate which collects in the bottom of frac- Ationator. 24 maybewithdrawnl therefrom and from the system for further treatment elsewherethrough line 30 provided with valve 3l.

The vaporous and gaseous fraction passing i overhead from fractionator24 is withdrawn therefrom through line 32 provided with control valve33. Line 32 connects with a fractionator 34 wherein the said gaseous andvaporous fraction is treated to effect the separation and collectiontherein of a normally liquid fraction desired for further treatment inaccordance with the process of the invention. Ordinarily the liquidfraction condensed in fractionator 34 will include substantially all theconstituents introtionator 43 are withdrawn overhead therefromthrough-line 4B provided with control valve 41. These gases may bewithdrawn kfrom the system for use elsewhere, for example, as fuel; orall or a portion thereof may be returned to the process through line 39as described above b ydiversion through line 43 which is provided with avalve 49 and connects lines 46 and 39.

When fractionator 34 is operated to effect con densation and collectionvof a liquid consisting substantially essentially of the relatively highboiling constituents of the motor fuel fraction, for

' example, those boiling above 300 F., the unconduced therein which arein the motor fuel boiling range and may include normally gaseoushydrocarbons such as C3 and C4 hydrocarbons in substantial proportions.However, if desired, the

liquid condensate separated in fractionator 34 may be limited to liquidsin the upper portion of For example, the

the gasolineboiling range. liquid condensate may be limited to excludesubstantially all constituents boiling below 300 F. To effect thedesired separation heating means such as heating coil 35 and coolingmeans such as cooling coil 36 may be provided in the bottom and top,respectively, of fractionator 34.

The disposal of the uncondensed fraction from Yfractionator 34 willdepend upon Athe conditions of operation of fractionator 34. Theuncondensed gases and any accompanying uncondensed vapors are withdrawnfrom fractionator 34 through line 31 provided with control valve 38.When the conditions of operation of fractionator 34 are controlled toeffect inclusion in the liquid fraction of substantially all convertiblenormally gaseous hydrocarbonssuch as Cs and C4 hydrocarbons theremaining gases taken overhead through line 31 may be withdrawn from thesystem for use elsewhere, for example, as fuel; or since these vgasesconsist essentially of methane and C2 hydrocarbons and may include.

unreacted carbon monoxide and hydrogen all or a portion thereof may bediverted from line 31 through line 39 provided with v alve 40. Line 39connects withline 5 whereby the mixture of hydrocarbon gases and carbonmonoxide and hv-A drogen are admixed with the oxygen-hydrocarbon-mixture in line 5 for passage to oxidation chamber 6." Suitableadjustment of the proportions of hydrocarbon gases and oxygen introducedthrough lines I and 3, respectively, may be efdensed portion withdrawnthrough line 31 will contain a substantial proportion of the motor fuelproduct of the process. To provide Separate recovery-of this portion ofthe motor fuel product a separate fractionator 50 is provided.Fractionator 50 is connected with line 31 by means of line 5| which isprovided with a valve 52. Line 5I connects with fractionator 50 at amiddle point thereof and with line 4| at a point between valve 42 andline 31. By closing valve 42 and opening valve 52 the overhead productfrom fractionator 34 passing through line 4l is diverted to fractionator50. In fractionator 50 conditions of Vtemperature and pressure aremaintained to fected by means of .valves 2 and 4 to maintain togetherwith any desired proportion of the C2 hydrocarbons. To effect thedesired fractionation heating means such as heating coil 44 and coolingor liquefaction means such as cooling coil 45 may be provided in thebottom and top, respectively,. `of fractionator 43. Gases uncondensed infrac-k effect the separation of that portion of the vapors desired inthe motor fuel product. Fractionator 50 may be provided with heatingmeans such as heating coil 53 and cooling means such as cooling coil 54in the bottom and top, respectively, thereof to effect the desiredfractionation. Gasesv uncondensed in fractionator 50 are withdrawntherefrom through line 55 provided with valve 56. Line 55 connects withline 4| between valve 42 and fractionator 43 whereby the latter may beused to effect separation in the manner described above of convertiblegaseous hydrocarbons from' the mixture passing through line 55.v Thegasoline constituents collected as liquid in the bottom of fractlonator50 are withdrawn therefrom through'lne 51 provided with a valve 58.

The liquid motor fuel fraction collected in the bottom of fractionator34 is withdrawn therefrom through line 59 `by means of pump 60 locatedin line 5 9 for further treatment in-accordance with the process of theinvention. Line 59 includes heat .exchanger I0 whereby thegnormallyliquid fraction is preheated by heat exchange with the` hot oxidationreaction products from charn-y ber 6. Line 59 connects with the inlet ofaheating coil 6| located in a furnace 62. If desired a heat exchanger 63may be provided in line 59 whereby the material 4passing therethrough isfurther 'preheated by heat exchange with the hot reaction productspassing from coil 6I.' Pref'-,

.erably coil BI is arranged in the furnace with a preheating sectionGla, a radiant heating section lband as oaking section @Ic in order toprovide the desired application of -heat to the material passingtherethrough. In accordance with the present invention normally gaseoushydrocarbons preferably predominating in C: and C4 hydrocarbons andcontaining substantial proportions of olenic constituents are admixedwith the liquid products of the carbon monoxide-hydrogen reaction beforeor during Vthe heat treatment,

provided in coil 6I. If desired these gaseous hy,-` drocarbons may beadmixed with the liquid material passing through line 59 prior topassage through heat exchanger I0. For example, they may be introducedthrough line 64 'which connects line 59 with a source to be describedbelow. Or'

the gaseous hydrocarbons may be introduced into norm-ally liquidhydrocarbons in line 59.

line 5I just previous to the passage ofthe liquid hydrocarbons throughheat exchanger 83. For example. the gaseous hydrocarbons may be'introduced to line 59 through line 55 which connects line 59 with asource to be described below.

If desired the' gaseous hydrocarbons may be` separately preheated beforeadmixture with the For example, gaseous hydrocarbons may be introducedby means of line 89 to the inlet of a separate heating coil 61 locatedinv a convection section of furnace 62. The preheated normally gaseoushydrocarbons emerge from the outlet of coil 61 through line 68 whichconnects with line 59 near the inlet of coil 8|. If desired, all or aportion of the preheated gaseous hydrocarbons from line 68 may bediverted through line 89 which connects line 68 with heating coil 8| ata point between preheater section 8 |c and radiant heating section 8|b.Valves 18 and 1I may be provided in lines l88 and 89, respectively, toaord4 the desired distributionof the preheated gaseous hydrocarbons toline 59 or through line 89. In the passage of the mixture of. normallyliquid and normally gaseous hydrocarbons through sections Elband Slo ofcoil 9| they are heated to a temperature sufficient to eiTect conversionto gasoline motor fuel constituents of high antiknock value. They may beheated to a temperature of 950 to 1200" F., for example i050" F., at apressure of 400 to 3000 pounds per square inch, for example 1000 poundsper square inch, for a time sumcient to effect the desired conversion.

The outlet of'the soaking section tlc which constitutes the outlet ofcoil 8| connects to line 12 through which the conversion reactionproducts from coil 9| are withdrawn. Line 12 includes heat exchanger93`whereby the hot re'- `action -products are partially cooleed by heatexchange with the fresh feed passing through line 59. Partially cooledreaction products may be further cooled by passage through heatexchanger 13 located in line 12 and also, if necessary, by further meanssuch 'as cooler 14 also located in line 12. It is to be understood.however, that the specific means of cooling the hot reaction productsshown are merely for purposes of illustration, and other means such asthe injection of cooling liquids directly into line 12 may be employed.Line 12 connects with an evaporator 15 which may be operated at the samepressure as maintained'in coil 8| or at a reduced pressure, controlvalve 18 being provided in line 12 to effect any desired reduction.

In separator 1I the reaction products are separated into a heavycondensate and uncondensed vapors and gases. 'I'he preliminary coolingof the reaction products and the operation of separator 15 arecontrolled to 'effect condensation and separation of relativelyhigh-boiling liquids.

For example, the material collected in separator 15 may have an initialboiling point of 600 to 650 F. To assist in the desired separationheating'means such as a heating coll 11 may be provided in the lowerportion of separator 15.

Suitable baille means may be provided in the may be provided withcontrol valve 8|. Line 88 connects with a fractionator 82 wherein themixture of gases and vapors is treated to enect sepaupper portion ofseparator 1l to remove liquidsy entrained in the uncondensed vapors andgases.

Y The condensate collected in the'bottom of separator 15 is withdrawntherefrom through line 18 which is provided with control valve 19. Thismaterial may -be used elsewhere, for example. as fuel. y

vapors and gases uncondensed in separator 15 are withdrawn therefromthrough line 88 which ration therefrom of normally liquid constituentshigher boiling than the desired motor fuel product and undesired forinclusion therein. This liquid condensate collects in the bottom offractionator 82 and is withdrawn therefrom through line 83 provided witha valve 84. 'I'his material may be subjected to further treatmentelsewhere as desired. For example, it may be subjected to elevatedconditions of temperature and pressure to convert it to gasoline motorfuel. Heating means such as heating coil 85 may be provided in the lowerportion of fractionator 82 to assist in the desired fractionation. Alsocooling means such as the introduction of reflux material in the upperportion of fractionator 82 through line 86 may be provided.

The vapors and liquids uncondensed in fractionator 82 are withdrawntherefrom through line 81 which is provided with control valve 88. Line81 contains a cooler 89 and connects with a collector 98. In cooler 89the gases and vapors are cooled to effect llquefactlon of constituentsdesired for inclusion in the motor fuel product of the process. Incollector 90 separation of liquids and uncondensed material is effected,the latter being'withdrawn through line 9| provided with control valve92 and the liquids being withdrawn through line 93 provided wlh controli valve 98. A portion of the liquids in line 93 may bediverted'therefrom forreturnl as reflux to frac' C: and lighterhydrocarbons as well as some C4 V hydrocarbons. 'I'hese gases preferablyare treated to eff ct separation therefrom of convertible constituentsfor further treat-ment in accordance with the process of the invention.For example, all or |a portion thereof may be diverted fromline 9|through line 95 provided with valve 95; or al1 or a portion thereof maybe diverted from line 9| through line 91 provided with a valve 98. Line91 connects with line 5 whereby the gaseous hydrocarbons passingtherethrough are admixed with the oxygen-hydrocarbon stream passingthrough line 5 to oxidation reaction chamber 8. ilSuitable adjustment ofthe proportions of hydrocarbon gases and oxygen introducedthroughlinesli and 3, respectively, may be eilected by meansof valves 2and 4 to maintain the proper ratio desired in the oxidation reactants.

Line 95 connects with the mid-point of a fractionator 89 whereintemperature and pressure conditions are maintained to effectv separationof a condensate consisting of convertible normally` gaseous hydrocarbonsauch as C: and C4 hydrocarbons. If necessary a compressor |88 may beVprovided in line 95 to transfer the gases smesso' r f 5 from the systemfor use elsewhere, for example,

as fuel: or all or a portion thereof may be diverted from line |03through line l|05 provided with valve |06. Line |06 connects line |09with line '91 whereby the uncondensed gases from fractionator 99 may bepassed to admixture with the oxidation reactants in line 6 as describedabove. v

The condensate which collects in the bottom of fractionator 99 willconsist for the most part of normally gaseous convertible hydrocarbonssuchv as C: and C4 hydrocarbons and will include subf Y stantialproportions of oleilns-Zormed as a result y of the reactions occurringin coil 6I. This material is withdrawn from fractionator -99 throughline |01 providedwith control valve |08. Line 66 which connects with theinlet lof coil 61 and includes heat exchanger 18 connects at its otherend with line |01 between fractionator 99 and valve |08. Line 66 isprovided with a control valve |09 and a pump H0 whereby, by manipulationof valves |08 and |09, any desired proportion of the condensate. from-fractionator 99 may be diverted through line 06 for passage'throughheat exchanger 13 and coil 61 as described above.

Line 64, which connects with line 59, connects at its otherend with line|01 between valve |08 and iractionator 99. Line 64 is provided with acontrol valve whereby all or a portion of the condensate fromfractionator 99 may be admixed with the condensate from fractionator 34,as dev scribed above.

The condensate` from fractionator 99, withdrawn therefrom through line|01, and undesired for passage through line 64 or line 66 may bewithdrawn from the system for use elsewhere, for

example, as fresh feed to a thermal or catalytic polymerization process.This material is par--v ticularly vuseful for such a process or forprocesses involving alkylation reactions sinceit includes substantialproportions of oleiinic` constituents. The decomposition of normallyliquid paraillnic l hydrocarbons incidental to the treatment of such Ymaterial in coil 6| promotes the decomposition b of normally gaseousparaiilnic hydrocarbons admixed therewith whereby the resulting reactionas heating coil H3 and cooling means in-the upper portion thereofsuch ascooling coil Ii@ to effect fractionation of the motor fuel productlintroduced through line 93 and produce amotor fuel containing thedesired proportion of light ends and normally-gaseous constituents. Thestabilized gasoline collected in the bottom thereof is withdrawnthroughline H5 provided with valve H6 andmay be withdrawn to storage. Ifdesired, this material may'be blended with the motor fuelproductwithdrawn from fractionator 50 through line 51 by means oi' lineI I1 which is provided with a` suitable control valve H8 and connectsline H5 and line 61.

'The operation of stabilizer H2 will 'depend upon the results desiredand upon the operation of other parts of the process. Ordinarily, itwill be operated to eilfect the production ,or a stabilized motor fuelincluding the desired proportionA V`V of normally gaseous constituents.However, it

'may be desired to include in the gases passing overheadall normallyrvgaseous constituents and even a portion of the lower boilingnormallyliquid'constituents of the motor fuel product. Thislatter methodlis particularly advantageous when the liquid ied to heating coil 6|includes only the heavier portion of the liquid constituents of the-vapors treated' in fractionator 34 and where it is desired to blend theliquid condensate from stabillzer II2 with the condensate fromfractionator 60, which latter condensate will ordinarily maintain anexcessive proportion of light ends. l c

It may also be advantageous to introduce into stabilizer I|2 allor aportion` of the condensate from fractionator 60 to eiect the productiontherein of a stabilized motor fuel. For example,

line l I9 provided with valve |20 may be provided 2.0 to connect line 51with stabilizer H2 at an intermediate point thereof.

The mixture of gases or gases and vapors produced in stabilizer H2 iswithdrawn from the y upper portion thereof through line I2| which isprovided with a compressor |22. Line |2| connects with line 66 wherebythe gases with accompanying vapors may be preheated in coil 81 andintroduced into coil 6| as described above; or all ora. portion of thegases and any accompanying vapors passing through line |2I may bediverted therefrom through line 65 which connects'line |2| with line 59as described above whereby the gases so diverted are admixed with theliquids passing through line 59. Valves .|22-

and |23' are provided in lines |2 and 65, re-

spectively, to provide the desired distribution to c lines 66 and 59.

The normally gaseous hydrocarbons separated as a condensate infractionator 43 may be employed in the process in addition to thoseproduced in fractionator 99 or stabilizer H2.. For I example, thecondensate from fractionator 43 may be Withdrawn therefrom through line|23 provided with valve |24. Line |23 connects with line 66 between pump|I|0`and valve |09 whereby the normally gaseous hydrocarbons fromfractionator 63 may be passed through line 66 and coil 61 as describedabove. If desired all or a. portion of the normally liquid hydrocarbonsmay be diverted from line |23 through line'l25 which is provided with avalve |26 and connects: with line 59 between pump 60 and fractionator 34whereby normally liquid hydrocarbons so divetted are admixed with thecondensate withdrawn from fractionator 39 for passage through line 59 tocoil 6|.

It is to be'understood that the various iractionators i5, 24, 34, 43,50, 82,99 and II2 are A provided with suitable gas yand liquid contactmeansA such las bubble trays to assist in the desired fractionation. Itis to be understood, furthermore, that the functions of the fractonatorillustrated may be carrled'out in a lesser-number of fractionators -withthe provision of suitable trap-out trays for withdrawal of side streams.However, for simplication in presenting the subject matter the presentarrangement is adopted for purposes of illustration.

The present invention provides a method forr the treatment of thereaction products of the4 carbon monoxide-hydrogen reaction to producetherefrom motor fuel of high anti-knock value under conditions ofmaximum emciency vand maximumrecovery of useful products. TheA inventionhas been described with reference to A.speclc combinations of steps, butitis to be understood that such reference is for the purpose ofillustration only, the invention not being necessarily limited thereto.'I'his application is a continuation-impart of my prior applicationSerial No. 119,178, filed January 6, 1937.

I claim:

l. 'Ihe method for converting the normally liquid and normally gaseoushydrocarbon products of the reaction of carbon monoxide and hydrogenwhich comprises separating from the said reaction products a fractionpredominating in normally liquid constituents and including at most aminor proportion of vhydrocarbons boiling above the gasoline boilingrange, admixing with said fraction a substantial proportion of normallygaseous hydrocarbons from a source set forth below, subjecting theresulting mixture to elegasoline of high anti-knock value, separatingfrom the resulting conversion products gasoline constituents. a normallygaseous fraction predominating in C: and C; hydrocarbons and a iixed gasfraction predominating 4in hydrocarbons containing less than threecarbon atoms per vated conditions of temperature and pressure to eii'ectconversion of normally liquid and normally gaseous constituents thereofto gasoline of high antiknock value, separating from the resultingconversion products gasoline constituents and a normally gaseousfraction predominating in C;

and C4 hydrocarbonspcontrolling the separation of the conversionproducts to etlect inclusion in said normally gaseous fraction of asubstantial proportion of therelatively low-boiling normally liquidconstituents of the said conversion products and admixing at least aportion of said gaseous fraction with said mst-mentioned fraction asdescribed.

2. The method of producing motor fuel of high anti-knock value whichcomprises subjecting normally gaseous hydrocarbons consistingessentially of hydrocarbons containing less than three carbon atoms permolecule tocatalytic oxidation to covert said hydrocarbons substantiallyto carbon monoxide and hydrogen. passing said car- `bon monoxide andhydrogen over a suitable catalyst and under suitable conditions oftemperature and pressure to `effect reaction of said carbon monoxideand'hydrogen to form hydrocarbons heavier than methane and/includingnormally liquid hydrocarbons, separating from the resulting reactionproducts a fraction predominating in normally liquid constituents andinclud ing at most a minor proportion of` hydrocarbons boiling above thegasoline boilingrange, admixing with'said fraction a substantialproportion of normally gaseous hydrocarbons from a source set forthbelow, subjecting the resulting mixture to elevated conditions oftemperature and pressure to effect conversion of normally liquid andnormally gaseous constituents thereof to molecule, admixing at least aportion of said A normally gaseous fraction with the fraction separatedfrom the carbon monoxide-hydrogen reaction products as described, andadmixing at least a portion of said nxed gas fraction with saidfirst-'mentioned normally gaseous hydrocarbons for processing therewith.v

3. 'I'he method for converting the normally liquid and normally gaseoushydrocarbon products of the reaction of carbon monoxide and hydrogenwhich comprises separating from the said reaction products a fractionpredominating in normally liquid constituents and including at mostaminor proportion of hydrocarbons boil ing in the upper portion of the'gasoline boiling range and hydrocarbons boiling above the gasolineboiling range, separating from said reaction products a second fractionpredominating in the normally liquid constituents and including at most'a minor proportion of hydrocarbons boilingin the lower portion ofthe-gasoline boil- .ing.range and hydrocarbons boiling above thegasoline bbiling range, admixing with said second fraction asubstantialproportion of normally gasous hydrocarbons from a sourceset forth below,subjecting the resulting mixture to elevated conditions of temperatureand pressure to eifect .conversion of normally liquid and normallygaseous constituents thereof to gasoline of high anti-knock value,separatingI from the resulting conversion products a gasoline fractiondeficient in constituents boiling in the lower portion of the gasolineboiling range and a vaporous fraction predominating in C: and `C4hydrocarbons and hydrocarbons boiling in theflower portion of thegasoline boiling range, suitably blending said last-mentioned gasolinefraction and' said first fraction to produce therefrom a stabilizedmotor fuel of high anti-knock value and admixing at least a 'portion.ofsaid vaporous'fraction with said second fraction prior to saidconversion treatment.-

4. 'Ihe method -inraccordance with claim 2 wherein C: and C4 hydrocarbonconstituents of the products of the reaction of carbon monoxide andhydrogen are passed to said thermal con.

' version treatment to eil'ect conversion thereof to gasoline of highanti-knock value.

' HAROLD V.l ATWEIL.

